New dinuclear hydrido-carbonyl rhenium complexes designed as photosensitizers in dye-sensitized solar cells

The possible use of some dinuclear rhenium complexes as sensitizers for dye sensitized solar cells (DSSCs) has been investigated. They have general formula [Re2(m-X)(m-Y)(CO)6(m-pyridazine-4-COOH)], with X = Y = Cl (1), X = H, Y = benzoato (2), and X = H, Y = 4-diphenylaminobenzoato (3). An original synthetic strategy has been set for preparing the hydrido-carboxylato derivatives 2 and 3. They have been indicated by DFT and TD-DFT computations as the most promising dyes, endowed with good light harvesting capability. The complexes have absorption maxima in the range of 405–443 nm, on TiO2 films, arising from metal-to-ligand-charge transfer transitions. Cyclic voltammetry experiments have been performed on the derivatives containing the methyl ester of the pyridazine-4-COOH acid, showing electrochemical band gaps in the range of 2.25–1.63 eV. The best DSSC results have been obtained using complex 3, with an overall solar-to-electric conversion efficiency of 1.0%. Noteworthy the presence of a hydrido ligand did not show any detrimental effect on the stability of the sensitizers under the operating conditions.